CN104220372B - Magnesium hydroxide particle and the resin combination that contains it - Google Patents
Magnesium hydroxide particle and the resin combination that contains it Download PDFInfo
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- CN104220372B CN104220372B CN201380017180.8A CN201380017180A CN104220372B CN 104220372 B CN104220372 B CN 104220372B CN 201380017180 A CN201380017180 A CN 201380017180A CN 104220372 B CN104220372 B CN 104220372B
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- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The resin combination that the invention provides a kind of purity and be magnesium hydroxide particles more than 98 quality % and contain it, described magnesium hydroxide is characterised in that, habit is hexagon prism shaped particles, described hexagon prism shaped particles is made up of the corner post face of the hexagonal base face of 2 faces up and down that are parallel to each other and 6 faces of periphery of forming between these basal surfaces, the size of the c-axis direction of aforementioned hexagon prism shaped particles is 0.5～1.5 μ m, the size of aforementioned c-axis direction is the more than 60% of median particle diameter of aforementioned hexagon prism shaped particles, flex point diameter is 0.1～0.4 μ m, intergranular space is 0.6 × 10-3～1.0×10-3m3·kg-1。
Description
Technical field
The resin combination that the present invention relates to magnesium hydroxide particle and contain it.
Background technology
Magnesium hydroxide can not produce toxic gas and environment excellence in the time of calcining, therefore can be used as resinThe fire retardant of composition and adding.
For magnesium hydroxide in the past, the micro crystal of magnesium hydroxide can be assembled, and forms aggregate particle sizeThe aggregation of average out to 10～100 μ m left and right. The magnesia that sets it as raw material manufacture also can only obtain grainThe particle that footpath is inhomogeneous. Therefore, in the time that above-mentioned magnesium hydroxide, magnesia are used as to the additive of resin,There is bad dispersibility, can not give full play to function or infringement resin physical property originally as additiveEtc. problem. In order to address this is that, propose to there is given shape to improve dispersiveness as objectMagnesium hydroxide (patent documentation 1).
But disclosed magnesium hydroxide is owing to making shape that variation occur, although therefore in patent documentation 1Improve to a certain extent dispersiveness, but still insufficient. And then, disclosed hydrogen-oxygen in patent documentation 1Change magnesium and contain subparticle, the inhomogeneous particle of crystal shape, therefore mixed as additive and synthetic resinWhen refining, exist resin viscosity easily rapidly rise, mobility, processability variation, shaping speed decline andThe problem of productivity ratio variation and so on.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-306659 communique
Summary of the invention
The problem that invention will solve
The object of the invention is to address the above problem, and the mobility while being compounded in resin is provided and dividesThe magnesium hydroxide particle that loose property is good and the resin combination that contains this magnesium hydroxide particle.
For the scheme of dealing with problems
In order to address the above problem, the inventor etc. have carried out various research repeatedly, found that, will be notContaining the particle of subparticle and irregular crystal shape and there is the magnesium hydroxide of uniform crystal shapeWhen particle is used as the additive of resin combination, can obtains excellent effect, thereby complete the present invention.In addition, the discoveries such as the inventor, iron that aforementioned magnesium hydroxide particle can contain ormal weight by use, vanadium,And the magnesium hydroxide slurry manufacture of manganese is for the magnesia of hydration reaction, and make this magnesia generation hydration andObtain.
That is, the present invention relates to a kind of purity is magnesium hydroxide particles more than 98 quality %, it is characterized in that,Habit is hexagon prism shaped particles, and described hexagon prism shaped particles is by 2 faces up and down that are parallel to each otherHexagonal base face and between these basal surfaces, be formed at 6 faces of periphery corner post face form, aforementioned sixThe size of the c-axis direction of corner post shaped particles is 0.5～1.5 μ m, and the size of aforementioned c-axis direction is aforementioned hexagonalThe more than 60% of the median particle diameter of post shapes particle, flex point diameter is 0.1～0.4 μ m, intergranular space is0.6×10-3～1.0×10-3m3·kg-1。
The present invention relates to aforesaid magnesium hydroxide particle, wherein, Fe content is 100～500ppm, V contentBe 30～250ppm, Mn content is 10～150ppm.
The present invention relates to aforesaid magnesium hydroxide particle, wherein, the mode diameter during pore distributes is0.1～0.3 μ m, mode volume is 2.3 × 10-3～2.8×10-3m3·kg-1。
The present invention relates to aforesaid magnesium hydroxide particle, its Zeta potential is-20～-25mV.
The present invention relates to a kind of manufacture method of magnesium hydroxide particle, it comprises following operation:
(a) in solvent, add magnesium hydroxide, iron compound, vfanadium compound and manganese compound and stirMix, obtain the operation of the slurry that comprises magnesium hydroxide, iron, vanadium and manganese, with respect to magnesium hydroxide, ironAddition be that the addition of 100～500ppm, vanadium is that the addition of 30～250ppm, manganese is10～150ppm；
(b) by the slurries filtration containing magnesium hydroxide, iron, vanadium and manganese, washing dry, obtain hydrogenThe coarse grained operation of magnesia;
(c) by magnesium hydroxide coarse granule in air atmosphere, calcine at 800～1900 DEG C, obtainThe operation of magnesium oxide particle; And
(d) add magnesium oxide powder to having added in the warm water of organic acid below 100 DEG C, then,High shear is carried out magnesian hydration reaction under stirring, the solid constituent that isolated by filtration generates then, andWash, be dried, obtain thus the operation of magnesium hydroxide particle, wherein, described magnesium oxide powder isMagnesium oxide particle is pulverized and sieved and obtains, and its median particle diameter is that 3～30 μ m, crystallite diameter are10×10-9More than m.
The present invention relates to a kind of resin combination, it contains (I) epoxy resin, (II) curing agent, (III)Inorganic filling material and (IV) as the aforementioned described magnesium hydroxide particle of fire retardant or by aforementionedDescribed manufacture method and the magnesium hydroxide particle that obtains.
The present invention relates to aforesaid resin combination, wherein, the compounding amount of aforementioned magnesium hydroxide particle is frontState 1～35 quality % of resin combination.
The present invention relates to aforesaid resin combination, it is encapsulation agent for semiconductor.
The present invention relates to a kind of semiconductor device, it uses aforesaid resin combination.
The effect of invention
According to the present invention, can obtain mobility while being compounded in resin and the magnesium hydroxide of favorable dispersibilityParticle and the resin combination that contains this magnesium hydroxide particle.
Brief description of the drawings
Fig. 1 is the key diagram that magnesium hydroxide particle profile of the present invention is shown.
Detailed description of the invention
1. magnesium hydroxide particle
Magnesium hydroxide particle of the present invention is hexagon prism shape as shown in Figure 1, the size of its c-axis direction(hereinafter referred to as " Lc ") is 0.5～1.5 μ m. In magnesium hydroxide particle of the present invention, Lc is preferably0.9～1.4 μ m. In addition, Lc is that Lc/d is with respect to the ratio of the median particle diameter (d) of magnesium hydroxide particleMore than 60%, Lc/d is preferably 60～150%, and more preferably 65～90%.
Lc/d is 60% when above, and magnesium hydroxide particle becomes good with respect to the mobility of resin. This tableThe value of showing Lc/d is larger, and the particle of hexagon prism shape reaches relatively all the more in c-axis direction. At magnesium hydroxide particleExist some to interact with the interface of resin, it is free-moving former that grain shape becomes constraint resinCause. Conventionally this tendency is subject to the impact of grain shape. That is to say, the degree of shape anisotropy becomes moreGreatly, impact becomes larger. Magnesium hydroxide particle of the present invention is due to following reason: it is along cThe particle that direction of principal axis is fully grown up, therefore little than shape anisotropy with Particle Phase in the past, hinder resinFree-moving essential factor few. It should be noted that, the median particle diameter d of magnesium hydroxide particle is as long as meetAforementioned Lc/d is just not particularly limited, and is conventionally preferably made as the scope of 0.1～10 μ m.
It should be noted that, the size of the c-axis direction of magnesium oxide particle is that Lc is utilizing scanning electronIn microscopical observation, there is the measured value of the particle of maximum length in the visual field. In addition, median particle diameter isAccumulation 50% while using laser diffraction and scattering formula particle size distribution device to measure, volume referenceParticle diameter (D50)。
The flex point diameter of magnesium hydroxide particle of the present invention is 0.1～0.4 μ m, and intergranular space is0.6×10-3～1.0×10-3m3·kg-1. In the present invention, flex point diameter and intergranular space can be according to pressing mercury formulaPore measure of spread is obtained. According to pore diameter and the accumulation pore of pressing the measure of spread of mercury formula pore to obtainThe relation curve of volume is called accumulation pore volume curve.
Particularly, press in the measure of spread of mercury formula pore, taking according to be pressed into pore diameter that pressure obtains asTransverse axis, taking accumulation pore volume as the longitudinal axis, mapping, obtains accumulation pore volume curve. By the pressure that is pressed into of mercuryPower to the conversion of pore diameter is used following (I) formula (Washburn formula) to convert.
D＝-(1/P)·4γ·cosψ(I)
Herein, D: pore diameter (m),
P: pressure (Pa)
γ: the surface tension (485dyne/cm (0.485Pam)) of mercury,
ψ: the contact angle (130 °=2.26893rad) of mercury.
Flex point diameter refers to pore diameter maximum in the flex point rising rapidly at accumulation pore volume curveThe pore diameter at some place. In addition, intergranular space is the accumulation pore volume at flex point diameter place. Flex point is straightWhen footpath and intergranular space are scope of the present invention, crystal shape and the particle diameter of magnesium hydroxide particle are even,And be aggregation, the few state of irregular crystal particle.
Flex point diameter is during lower than 0.1 μ m, and magnesium hydroxide particle contains and has the micro-of inhomogeneous crystal shapeFine grained. Therefore, flex point diameter is set with synthetic as additive lower than the magnesium hydroxide particle of 0.1 μ mWhen fat is mixing, resin viscosity rises rapidly, mobility variation. In addition, when flex point diameter exceedes 0.4 μ m,The crystal shape of a part of particle of magnesium hydroxide particle becomes irregular, and particle becomes easy gathering, meetingForm thick particle. Therefore the particle that, flex point diameter is exceeded to 0.4 μ m is as additive and synthetic treeWhen fat is mixing, can form thick aggregation, particle is easily sedimentation in resin, can hinder mobility,Processability. In the present invention, flex point diameter is preferably 0.2～0.3 μ m.
Intergranular space is lower than 0.6 × 10-3m3·kg-1Time, magnesium hydroxide particle contains and has inhomogeneous crystal shapeThe subparticle of shape. Therefore, by intergranular space lower than 0.6 × 10-3m3·kg-1Particle as additive withWhen synthetic resin is mixing, resin cannot infiltrate into granule interior, the not fully decentralized particle of easy formation,Space. And, also variation thereupon of mobility. In addition, intergranular space exceedes 1.0 × 10-3m3·kg-1Time,The crystal shape of a part of particle of magnesium hydroxide becomes irregular, and particle becomes easy gathering, can formThick particle. Therefore, intergranular space is exceeded to 1.0 × 10-3m3·kg-1Magnesium hydroxide particle as addingAdd agent and synthetic resin when mixing, can form thick aggregation, particle is easily sedimentation in resin, meetingHinder mobility, processability. In the present invention, intergranular space is preferably 0.7 × 10-3～0.9×10-3m3·kg-1。
The purity of magnesium hydroxide particle of the present invention is more than 98.0 quality %. During for this scope, can be extremelyThe stripping of inhibition of impurities, can make as the additive of the resin as high functionality material aptlyWith. The purity of magnesium hydroxide particle of the present invention is preferably 98.5～99.9 quality %.
In this description, purity be impurity element in determination object particle (Ag, Al, B, Ba, Bi,Cd、Cl、Co、Cr、Cu、Fe、Ga、In、K、Li、Mn、Mo、Na、Ni、P、Pb、S、Si, Sr, Tl, V, Zn, Ti and Zr) content, and from 100 quality %, deduct their total contentThe value obtaining. For become determination object impurity element (Ag, Al, B, Ba, Bi, Cd, Co,Cr、Cu、Fe、Ga、In、K、Li、Mn、Mo、Na、Ni、P、Pb、S、Si、Sr、Tl、V, Zn, Ti and Zr), use ICP emission spectrographic analysis device, sample is dissolved in after acid, measure itQuality, Cl amount is to use spectrophotometer, and sample is dissolved in to the value that its quality of the rear mensuration of acid obtains.
The content of the preferred iron of magnesium hydroxide particle of the present invention (Fe) is 100～500ppm, vanadium (V)Content is 30～250ppm, and the content of manganese (Mn) is 10～150ppm. The content of Fe be 100～500ppm,The content of V is the content of 30～250ppm, Mn while being 10～150ppm, the crystal shape of magnesium hydroxide particleShape easily forms uniform shape, and can extremely suppress the stripping of metal impurities, conduct aptlyAdditive, for example fire retardant use. More preferably the content of Fe is 150～400ppm, and the content of V is60～120ppm, the content of Mn is 40～80ppm.
The preferred mode diameter of magnesium hydroxide of the present invention is 0.1～0.3 μ m. In addition, hydroxide of the present inventionThe preferred mode volume of magnesium granules is 2.3 × 10-3～2.8×10-3m3·kg-1. As long as be such mode diameter and crowdNumber volume, the crystal shape of magnesium hydroxide particle and particle diameter are more even, from being aggregation, irregularIt is preferred that the viewpoint of the few state of crystal grain is set out.
Mode volume of the present invention and mode diameter can be according to pressing the measure of spread of mercury formula pore to obtain, thisPlace's mode volume is the maximum of log differential pore volume distribution curve, and mode diameter is log differential poreThe corresponding pore diameter of maximum of volume distribution curve. Measure hydroxide of the present invention by mercury injection methodWhen the pore of magnesium granules distributes, mode diameter is corresponding to the diameter in the space between magnesium hydroxide particle.
The preferred Zeta potential of magnesium hydroxide particle of the present invention is-20～-25mV, more preferably-21～-25mV. As long as Zeta potential is this scope, the dispersiveness in resin becomes better,Can obtain sufficient mobility.
2. the manufacture method of magnesium hydroxide particle of the present invention
Magnesium hydroxide particle of the present invention for example can be manufactured as described below.
First, in solvent, add magnesium hydroxide, iron compound, vfanadium compound and manganese compound and stirMix, obtain the slurry containing magnesium hydroxide, iron, vanadium and manganese, after filtration washing, make it dry, obtain hydrogenMagnesia coarse granule. Then, this magnesium hydroxide coarse granule is calcined in the scope of 800～1900 DEG C,Obtain thus raw materials of magnesium oxide. Then, add oxygen to having added in the warm water of organic acid below 100 DEG CChange magnesium dust, under high shear is stirred, carry out the hydration reaction of magnesium oxide powder, by the solid constituent generatingIsolated by filtration, wash and make it dry, obtaining the magnesium hydroxide that manufacturing method according to the invention is producedGrain, wherein, described magnesium oxide powder is pulverized this raw materials of magnesium oxide sieve and obtains its intermediate valueParticle diameter is that 3～30 μ m, crystallite diameter are 10 × 10-9More than m.
Particularly, the manufacture method of magnesium hydroxide particle of the present invention comprises following operation:
(a) in solvent, add magnesium hydroxide, iron compound, vfanadium compound and manganese compound and stirMix, obtain the operation containing the slurry of magnesium hydroxide, iron, vanadium and manganese, with respect to magnesium hydroxide, ironAddition is that the addition of 100～500ppm, vanadium is that the addition of 30～250ppm, manganese is 10～150ppm;
(b) by the slurries filtration containing magnesium hydroxide, iron, vanadium and manganese, washing and dry, obtain hydrogenThe coarse grained operation of magnesia;
(c) by magnesium hydroxide coarse granule in air atmosphere, calcine at 800～1900 DEG C, obtainThe operation of magnesium oxide particle; And
(d) add magnesium oxide powder to being added with in the warm water of organic acid below 100 DEG C, then at heightUnder shear agitation, carry out magnesian hydration reaction, the solid constituent that isolated by filtration generates then, goes forward side by sideRow washing, dry, obtains the operation of magnesium hydroxide particle thus, wherein, described magnesium oxide powder be byMagnesium oxide particle is pulverized and is sieved and obtains, and its median particle diameter is that 3～30 μ m, crystallite diameter are10×10-9More than m.
(1) operation (a)
Operation (a) is in solvent, to add magnesium hydroxide, iron compound, vfanadium compound and manganese to closeThing also stirs, and obtains the operation containing the slurry of magnesium hydroxide, iron, vanadium and manganese, with respect to magnesium hydroxide,The addition of iron is that the addition of 100～500ppm, vanadium is that the addition of 30～250ppm, manganese is10～150ppm。
As the magnesium hydroxide using in operation (a), if for purity more than 95%, median particle diameterBe the magnesium hydroxide of 0.5～50 μ m left and right, be just not particularly limited. There is the hydroxide of this median particle diameterMagnesium can be by shattering commercially available jar mill for magnesium hydroxide (potmill) etc. to obtain. As commercially availableMagnesium hydroxide, for example can list TatehoChemicalIndustriesCo., Ltd manufactureMAGSTAR#20, MAGSTAR#4, MAGSTAR#5 and MAGSTAR#2.
As iron compound, can list iron oxide (ferrous oxide and di-iron trioxide), iron hydroxide,Ferric carbonate, iron chloride and ferric nitrate, preferential oxidation iron. Iron compound can use separately, also can groupClose and use multiple iron compound.
As vfanadium compound, can list vanadium oxide, vanadium hydroxide, carbonic acid vanadium, vanadium chloride and nitric acid vanadium,Preferential oxidation vanadium. Vfanadium compound may be used alone, can also be used in combination multiple vfanadium compound.
As manganese compound, can list manganese oxide, manganous hydroxide, manganese carbonate, manganese chloride and manganese nitrate,Preferential oxidation manganese. Manganese compound may be used alone, can also be used in combination multiple manganese compound.
As solvent, can list ion exchange water. To comprising the slurry of magnesium hydroxide, iron, vanadium and manganeseThe concentration of the magnesium hydroxide in material is not particularly limited, and is preferably below 50 % by weight more preferably 10～40% by weight.
For the consumption of iron compound, vfanadium compound and manganese compound, with respect to magnesium hydroxide, the adding of ironDosage is 100～500ppm, and the addition that is preferably 150～400ppm, vanadium is 30～250ppm, preferablyThe addition that is 60～120ppm, manganese is 10～150ppm, is preferably 40～80ppm. As long as meeting becomesIron compound, vfanadium compound and the manganese of the addition of the addition of such iron, the addition of vanadium and manganeseThe consumption of compound, by calcining and further hydration operation, can obtain the hydrogen with uniform crystal shapeMagnesium oxide particle, and flex point diameter and intergranular space are included in magnesium hydroxide particle of the present invention and sayIn bright scope.
In the present invention, sometimes contain iron, vanadium, manganese as the magnesium hydroxide of raw material. In this case, pre-First measure the content as the iron in the magnesium hydroxide of raw material, vanadium, manganese, then with respect to magnesium hydroxideThe addition of iron, vanadium and the manganese mode that is aforementioned quantities add iron compound, vfanadium compound and manganese and closeThing also stirs, and can obtain thus the slurry that comprises magnesium hydroxide, iron, vanadium and manganese.
Stirring for example can be at 10～50 DEG C, carry out 0.5～5 hour with the rotary speed of 100～800rpm.
(2) operation (b)
Operation (b) is by the slurries filtration that comprises magnesium hydroxide, iron, vanadium and manganese, washing and dry,Obtain the coarse grained operation of magnesium hydroxide. Thus, can obtain the hydrogen that comprises iron, vanadium and manganese before calciningMagnesia coarse granule. Magnesium hydroxide coarse granule before calcining contain from containing magnesium hydroxide, iron, vanadium andIron, vanadium and the manganese of the slurry of manganese. Filtration can be carried out with filter paper etc., and washing can be by dropping intoCounting the pure water of 5～100 times with respect to magnesium hydroxide with quality criteria carries out.
(3) operation (c)
Operation (c) be by the magnesium hydroxide coarse granule obtaining in operation (b) in atmospheric atmosphere,At 800～1900 DEG C, calcine, obtain the operation of magnesium oxide particle. The coarse grained calcining of magnesium hydroxide canWith by for example in atmospheric atmosphere, with 1～20 DEG C/min, be preferably the programming rate of 3～10 DEG C/minBe warming up to 800～1900 DEG C, be preferably 1000～1500 DEG C, after intensification 800～1900 DEG C, be preferablyAt 1000～1500 DEG C, calcine and carry out for 0.1～5 hour.
(4) operation (d)
Operation (d) is to add magnesium oxide powder to being added with in the warm water of organic acid below 100 DEG C, connectsUnder high shear is stirred and carry out magnesian hydration reaction, the solid that isolated by filtration generates then becomesPoint, and wash, be dried, obtain thus the operation of magnesium hydroxide particle, wherein, described magnesiaPowder is pulverized magnesium oxide particle sieve and is obtained, and its median particle diameter is 3～30 μ m, and crystallite is straightFootpath is 10 × 10-9More than m.
The median particle diameter of magnesium oxide powder that hydration reaction is used, that pulverize and sieve and obtain is3～30 μ m, are preferably 5～20 μ m, more preferably 5～15 μ m. As long as use the magnesia conduct of this scopeRaw material, just can fully carry out hydration reaction, obtains the magnesium hydroxide of target sizes and not residual incompleteCarry out the magnesia of hydration reaction. In addition, crystallite diameter is 10 × 10-9More than m, be preferably10×10-9～40×10-9M, more preferably 10 × 10-9～30×10-9M. If the magnesia of this scope is used forRaw material, reaction speed when hydration is suppressed, and can not form thick aggregated particle. Need explanation, crystallite diameter refers to the value that uses X-ray diffraction method, calculates according to Scherrer formula.
Organic acid adds as the solubility of the magnesium oxide powder of raw material in order to suppress. As organicAcid, can list aliphatic or the aromatic organic acid with carboxyl, preferable formic acid, acetic acid, propionic acid,Butyric acid and benzoic acid. With respect to the magnesium oxide powder 100g using in operation (d), organic acid addsDosage is preferably 0.01～3.0mol, more preferably 0.01～0.30mol. Such amount, crystal ifSpeed of separating out be suitably, the deviation of the median particle diameter of the magnesium hydroxide particle of acquisition is few.
Hydration reaction can be below 100 DEG C, for example under the middle and high shear agitation of warm water of 50～100 DEG C, enterOK. The temperature of warm water is preferably 60～100 DEG C. As the water for warm water, for fear of sneaking into of impurity,Preferred ion exchanged water. High shear is stirred as long as fully carry out for magnesian hydration reaction, can obtain the phaseThe stirring extent of magnesium hydroxide slurry of hoping, for example, can possess by use the high speed of turbo bladeMixer carries out. The peripheral speed of mixer is preferably 8～18m/s, more preferably 9～15m/s. Incorporation timeCan change according to magnesian hydration reaction degree, for example, can be made as 0.5～6 hour.
By above-mentioned operation, can obtain the magnesium hydroxide particle that utilizes manufacture method of the present invention to manufacture. LogicalThe magnesium hydroxide particle of crossing manufacture method acquisition of the present invention is preferably magnesium hydroxide particle of the present invention.
Magnesium hydroxide particle of the present invention can, by implementing various surface treatments, improve the parent to resinWith functions such as property, acid resistance, water repellency, ultraviolet-absorbings. Magnesium hydroxide particle of the present invention as aboveDispersion in resin becomes well describedly, is giving function as described above by surface treatmentIn situation, also can give full play to this function.
As for improving and the surface conditioning agent of the compatibility of resin, for example, can list higher fatty acidsOr the fatty acid ester of its alkali metal salt, phosphate, silane coupler class, polyalcohol etc. In addition, forRaising acid resistance, water repellency etc., for example can utilize the hydrolysis of methyl silicate, silesterSilica-coating, utilizes the coating of silicone oil, Polyfluoroalkyl phosphate ester salt etc. In addition, in order to improve purpleOutside line absorbability, thus for example can make locating of titanyl sulfate generation hydrolysis coating titanium dioxideReason. Aforementioned surfaces is processed and also can be combined multiple carrying out.
3. resin combination
Resin combination of the present invention contains (I) epoxy resin, (II) curing agent, (III) inorganic fillMaterial and (IV) as the magnesium hydroxide particle of the present invention of fire retardant or by manufacture of the present inventionThe magnesium hydroxide particle that method obtains.
As the epoxy resin of composition (I), be not particularly limited, can use known epoxy resin.Particularly, can list bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresols phenolNovolac type epoxy resin, biphenyl type epoxy resin etc., preferably cresols phenolic resin varnish type epoxy resin.
As the curing agent of composition (II), be not particularly limited, can use known curing agent, exampleAs listed phenolic resins, acid anhydrides, amines, preferably phenolic resins.
As the inorganic filling material of composition (III), for example can list quartz glass powder, talcum,SiO 2 powder, alumina powder, calcium carbonate, boron nitride, silicon nitride and hydrocarbon black powder etc. Wherein,Preferably SiO 2 powder, particularly preferably spherical silicon dioxide powder, most preferably spheroidal fused silicaPowder.
Resin combination of the present invention can be by magnesium hydroxide particle of the present invention or by manufacture of the present inventionThe magnesium hydroxide particle that method obtains and (I) epoxy resin, (II) curing agent, (III) inorganic fill materialMaterial waits together mixing and obtain. In this resin combination, the compounding amount of flame retardant of magnesium hydroxide is preferably tree1～35 quality % of oil/fat composition entirety, further preferably, the total of inorganic matter, i.e. magnesium hydroxideMore preferably 60～95 matter of resin combination entirety of the total compounding amount of additive and inorganic filling materialAmount %.
The anti-flammability of above-mentioned resin combination, moisture-proof, acid resistance etc. are environment resistant also excellent, as halfConductor is useful with encapsulation agent, therefore can manufacture and utilize this resin combination to carry out the various of encapsulationSemiconductor device.
As long as resin composition for sealing semiconductor can be by dispersed various raw material mixing, just to itPreparation method is not particularly limited. If list concrete example, for example, can make following various formsGoods: utilize mixer etc. fully to mix, after the melting mixing such as mixing mill, extruder, enterRow is cooling, pulverizing, by making it be shaped to the goods that graininess forms, according to the size that meets condition of moldingAnd the goods that form of weight compressing tablet, or the mixture of each composition of above-mentioned resin combination is accommodated inOn supporting plate, it is cooling after by compacting roll, roll-in prolongs, maybe enter having mixed the material that solvent formsThereby the method for row coating sheet etc. is shaped to laminar goods etc.
The envelope of the semiconductor element of the resin composition for sealing semiconductor obtaining using operation like thisDress method is not particularly limited, for example, can use the known forming methods such as common transfer molding.
Embodiment
Be described more specifically the present invention by embodiment, but the present invention is not limited to following embodiment.
The magnesium hydroxide particle obtaining in embodiment and the median particle diameter of magnesium oxide particle, Lc, purity andPore distribution (flex point diameter, intergranular space, mode volume, mode diameter) comes by the following methodMeasure.
(1) mensuration of Lc
The Lc of the particle to maximum length have the visual field in scanning electron microscope is observed in surveysFixed.
(2) median particle diameter (the accumulation 50% particle diameter (D of volume reference50)) mensuration
Use laser diffraction and scattering formula particle size distribution device (trade name: MT3300, day machine dress strainFormula commercial firm manufactures) mensuration median particle diameter.
(3) the quality determination method of the impurity element in magnesium hydroxide
For the impurity element as determination object (Ag, Al, B, Ba, Bi, Cd, Co, Cr,Cu、Fe、Ga、In、K、Li、Mn、Mo、Na、Ni、P、Pb、S、Si、Sr、Tl、V、Zn, Ti and Zr), use ICP emission spectrographic analysis device (trade name: SPS-5100, SeikoInstrumentsInc. manufacture), sample is dissolved in to the rear quality measurement of acid.
For Cl amount, use spectrophotometer (trade name: UV-2550, Shimadzu Seisakusho Ltd. manufacture), willSample is dissolved in the rear quality measurement of acid.
(4) purity testing method
The purity of magnesium hydroxide is as deducting according to the above-mentioned " impurity magnesium hydroxide from 100 quality %The quality determination method of element " impurity element measured quality total and the value that obtains calculates.
(5) survey of pore distribution (flex point diameter, intergranular space, mode volume and mode diameter)Fixed
By flex point diameter, intergranular space, the log differential pore of pressing the measure of spread of mercury formula pore to obtain(mode is straight for the maximum (mode volume) of volume distribution curve and the corresponding pore diameter of mode volumeFootpath) obtain according to following condition. Press mercury formula pore measure of spread device to use MicroMetrics company systemThe AutoPore9410 making measures. Mercury use purity 99.5mass% is above, density 13.5335 × 103kg/m3Superfine mercury reagent. Measure pipe (cell) and use pipe internal volume 5 × 10-6m3, neck (stem)Volume 0.38 × 10-6m3Powdered sample with pipe. For measuring sample, in quality 0.10 × 10-3～0.13×10-3In the scope of kg precision weighing use in advance 330 mesh standard sieves (JIS-R8801-87) regular the sample of particle diameter,And be filled in mensuration pipe. Mensuration pipe is installed on after device, will manages inner at pressure 50 μ Hg (6.67Pa)Below keep 20 minutes decompression states. Then, fill mercury until pressure reaches 1.5psia to measuring in pipe(10342Pa) till. At pressure be, 2psia (13790Pa) to 60000psia (413.7MPa) thereafterScope in be pressed into mercury, measure pore distribute.
In order to be pore diameter by the conversion pressure that is pressed into of mercury, use following (I) formula.
D＝-(1/P)·4γ·cosψ(I)
Herein, D: pore diameter (m),
P: mercury be pressed into pressure (Pa),
γ: the surface tension (485dynecm of mercury-1(0.485Pa·m))、
ψ: the contact angle (130 °=2.26893rad) of mercury.
[embodiment 1]
The manufacture > of < magnesium hydroxide particle
In container, adding purity more than 95%, median particle diameter is the magnesium hydroxide of 5.9 μ m and with respect to hydrogenMagnesia makes iron oxide that the addition of Fe is 200ppm, make vanadium oxide that the addition of V is 100ppm,Manganese oxide that the addition that makes Mn is 50ppm, to make the concentration of magnesium hydroxide be the ion below 30 % by weightExchanged water also stirs. Then, the white precipitate of acquisition is filtered, washed and is dried. This is dryThing is pulverized with ball mill, uses electric furnace at 1400 DEG C, to calcine 2 hours. By this calcined material ball mill powderAfter broken 4 hours, carry out classification, obtain magnesium oxide powder. The median particle diameter of the magnesium oxide powder obtaining is10.2 μ m, crystallite diameter is 28.9 × 10-9m。
The magnesium oxide powder of acquisition is added to the internal volume 20L of the acetic acid 10L that concentration 0.02mol/L is housedContainer in, making oxide (MgO) concentration is 100g/L. On one side by mixing containing magnesian of obtainingClose solution and remain on 90 DEG C, use on one side homogenizer (special Ji Hua Co., Ltd. manufactures, trade name:Homomixer), the rotating speed of turbo blade is made as to 10m/s, stirs while to carry out hydration in 4 hours anti-Should. , filter, wash, be dried, obtain magnesium hydroxide particle thereafter.
For the magnesium hydroxide particle obtaining, magnesium hydroxide purity is 98.8 quality %, during pore distributesFlex point diameter is 0.22 μ m, and intergranular space is 0.88 × 10-3m3·kg-1, mode diameter is 0.17 μ m, crowdNumber volume is 2.51 × 10-3m3·kg-1。
< evaluation test >
This magnesium hydroxide particle is mixing according to ratio shown in table 1 and epoxy resin, and according to following conditionMeasure eddy flow (spiralflow) and the anti-flammability of the resin combination obtaining. Herein, eddy flow is for representingThe value of the mobility of thermoplastic resin composition and compositions of thermosetting resin. Wherein, use cresols phenolic aldehydeVarnish type epoxy resin (epoxide equivalent 198) is as epoxy resin, use phenol novolac resin (hydroxylBase equivalent 105) as curing agent, use triphenylphosphine as curing accelerator, use spheroidal fused twoSilica is as inorganic filling material.
[table 1]
| [formula] | |
| Epoxy resin | 25.6g |
| Curing agent | 13.6g |
| Flame retardant of magnesium hydroxide | 38.0g |
| Inorganic filling material | 125.0g |
| Curing accelerator | 0.4g |
| Metal hydroxides ratio | 18.8％ |
| Inorganic matter ratio | 80.5％ |
(1) anti-flammability assay method
Use composition epoxy resin, manufacture 1/16 inch of thickness flame retardant test sheet (condition of molding:175 DEG C of temperature, 120 seconds of time, solidify (postcure) 175 DEG C × 6 hours afterwards), according to UL-94V-0The method evaluation anti-flammability of standard.
(2) eddy flow assay method
Use eddy flow mensuration mould, under the condition of 175 DEG C of temperature, pressure 6086MPa, according to EMMI1-66 measures eddy flow value.
(3) assay method of Zeta potential
Magnesium hydroxide particle 0.003g is carried out in ultra-pure water 300ml after ultrasonic wave dispersion in approximately 10 minutes,Use laser Zeta potential meter ELS-8000 (OtsukaElectronicsCo., Ltd. manufactures) to measure.Measuring temperature is 25 DEG C, and assay method is electrophoretic light scattering method.
[embodiment 2]
In container, add more than 95% magnesium hydroxide of the purity using in embodiment 1 and make magnesium hydroxideIn the addition of the Fe iron oxide that is 100ppm, make vanadium oxide that the addition of V is 100ppm, makeThe addition of Mn is the manganese oxide of 50ppm, and the concentration that makes magnesium hydroxide is that the ion below 30 % by weight is handed overChange water and stir. Then, the white precipitate obtaining is filtered, washes and be dried. By this dry thing ballGrinding machine is pulverized, and uses electric furnace at 1400 DEG C, to calcine 2 hours. This calcined material is pulverized 8 hours with ball millAfter, carry out classification, obtain magnesium oxide powder. The median particle diameter of the magnesium oxide powder obtaining is 6.8 μ m,Crystallite diameter is 29.9 × 10-9m。
The magnesium oxide powder of acquisition is added to the internal volume 20L of the acetic acid 10L that concentration 0.03mol/L is housedContainer in, making oxide (MgO) concentration is 100g/L. On one side by mixing containing magnesian of obtainingClose solution and remain on 90 DEG C, (Japanese special Ji Hua Co., Ltd. manufactures, business to use on one side homogenizerThe name of an article: Homomixer), the rotating speed of turbo blade is made as to 10m/s, stir while carry out 4 hoursHydration reaction. , filter, wash, be dried, obtain magnesium hydroxide particle thereafter.
For the magnesium hydroxide particle obtaining, magnesium hydroxide purity is 98.7 quality %, during pore distributesFlex point diameter is 0.27 μ m, and intergranular space is 0.75 × 10-3m3·kg-1, mode diameter is 0.24 μ m, crowdNumber volume is 2.47 × 10-3m3·kg-1。
[comparative example 1]
Do not add iron oxide, vanadium oxide and manganese oxide, in container, add the purity using in embodiment 1More than 95% magnesium hydroxide particle is the ion exchange water below 30 % by weight with making the concentration of magnesium hydroxideAnd stir. Then, the white precipitate obtaining is filtered, washes and be dried. By this dry thing ball millPulverize, use electric furnace at 1400 DEG C, to calcine 2 hours. This calcined material is pulverized after 4 hours with ball mill,Carry out classification, obtain magnesium oxide powder. The median particle diameter of the magnesium oxide powder obtaining is 11.2 μ m, crystalliteDiameter is 30.9 × 10-9m。
The magnesium oxide powder of acquisition is added to the internal volume 20L of the acetic acid 10L that concentration 0.03mol/L is housedContainer in, making oxide (MgO) concentration is 100g/L. On one side by mixing containing magnesian of obtainingClose solution and remain on 90 DEG C, use on one side homogenizer (special Ji Hua Co., Ltd. manufactures, trade name:Homomixer), the rotating speed of turbo blade is made as to 10m/s, stirs while to carry out hydration in 4 hours anti-Should. , filter, wash, be dried, obtain magnesium hydroxide particle thereafter.
For the magnesium hydroxide particle obtaining, magnesium hydroxide purity is 98.2 quality %, during pore distributesFlex point diameter is 0.14 μ m, and intergranular space is 0.59 × 10-3m3·kg-1, mode diameter is 0.08 μ m, crowdNumber volume is 2.34 × 10-3m3·kg-1。
[comparative example 2]
In container, add in embodiment 1 more than 95% magnesium hydroxide of the purity using and with respect to hydrogen-oxygenChanging magnesium makes iron oxide that the addition of Fe is 300ppm, makes vanadium oxide that the addition of V is 300ppm, makesThe addition of Mn be 250ppm manganese oxide, to make the concentration of magnesium hydroxide be the ion below 30 % by weightExchanged water also stirs. Then, the white precipitate obtaining is filtered, washes, is also dried. By this dry thingPulverize with ball mill, use electric furnace at 1400 DEG C, to calcine 2 hours. This calcined material is pulverized to 4 with ball millAfter hour, carry out classification, obtain magnesium oxide powder. The median particle diameter of the magnesium oxide powder obtaining is10.61 μ m, crystallite diameter is 25.9 × 10-9m。
The magnesium oxide powder of acquisition is added to the internal volume 20L of the acetic acid 10L that concentration 0.03mol/L is housedContainer in, making oxide (MgO) concentration is 100g/L. On one side by mixing containing magnesian of obtainingClose solution and remain on 90 DEG C, use on one side homogenizer (special Ji Hua Co., Ltd. manufactures, trade name:Homomixer), the rotating speed of turbo blade is made as to 10m/s, stirs while to carry out hydration in 4 hours anti-Should. , filter, wash, be dried, obtain magnesium hydroxide particle thereafter.
For the magnesium hydroxide particle obtaining, magnesium hydroxide purity is 98.8 quality %, during pore distributesFlex point diameter is 0.49 μ m, and intergranular space is 1.1 × 10-3m3·kg-1, mode diameter is 0.34 μ m, crowdNumber volume is 2.86 × 10-3m3·kg-1。
[comparative example 3]
In container, add in embodiment 1 more than 95% magnesium hydroxide of the purity using and with respect to hydrogen-oxygenChange magnesium and make iron oxide that the addition of Fe is 200ppm, make the manganese oxide that the addition of Mn is 50ppm,The concentration that makes magnesium hydroxide is the ion exchange water below 30 % by weight and stirs. Then, white by what obtainLook sedimentation and filtration, washing, also dry. This dry thing is pulverized with ball mill, used electric furnace at 1400 DEG CLower calcining 2 hours. This calcined material is pulverized after 4 hours with ball mill, carried out classification, obtain magnesia powderEnd. The median particle diameter of the magnesium oxide powder obtaining is 11.52 μ m, and crystallite diameter is 28.9 × 10-9m。
The magnesium oxide powder of acquisition is added to the internal volume 20L of the acetic acid 10L that concentration 0.03mol/L is housedContainer in, making oxide (MgO) concentration is 100g/L. On one side by mixing containing magnesian of obtainingClose solution and remain on 90 DEG C, use on one side homogenizer (special Ji Hua Co., Ltd. manufactures, trade name:Homomixer), the rotating speed of turbo blade is made as to 10m/s, stirs while to carry out hydration in 4 hours anti-Should. , filter, wash, be dried, obtain magnesium hydroxide particle thereafter.
For the magnesium hydroxide particle obtaining, magnesium hydroxide purity is 98.7 quality %, during pore distributesFlex point diameter is 0.48 μ m, and intergranular space is 1.25 × 10-3m3·kg-1, mode diameter is 0.38 μ m, crowdNumber volume is 2.92 × 10-3m3·kg-1。
[comparative example 4]
In container, add in embodiment 1 more than 95% magnesium hydroxide of the purity using and with respect to hydrogen-oxygenChanging magnesium makes iron oxide that the addition of Fe is 200ppm, makes vanadium oxide that the addition of V is 100ppm, makesThe concentration of magnesium hydroxide is the ion exchange water below 30 % by weight and stirs. Then, by the white obtainingSedimentation and filtration, washing, also dry. This dry thing is pulverized with ball mill, used electric furnace at 1400 DEG CCalcine 2 hours. This calcined material is pulverized after 4 hours with ball mill, carried out classification, obtain magnesium oxide powder.The median particle diameter of the magnesium oxide powder obtaining is 10.24 μ m, and crystallite diameter is 29.1 × 10-9m。
The magnesium oxide powder of acquisition is added to the internal volume 20L of the acetic acid 10L that concentration 0.03mol/L is housedContainer in, making oxide (MgO) concentration is 100g/L. On one side by mixing containing magnesian of obtainingClose solution and remain on 90 DEG C, use on one side homogenizer (special Ji Hua Co., Ltd. manufactures, trade name:Homomixer), the rotating speed of turbo blade is made as to 10m/s, stirs while to carry out hydration in 4 hours anti-Should. , filter, wash, be dried, obtain magnesium hydroxide particle thereafter.
For the magnesium hydroxide particle obtaining, magnesium hydroxide purity is 98.2 quality %. During pore distributesFlex point diameter is 0.42 μ m, and intergranular space is 1.33 × 10-3m3·kg-1, mode diameter is 0.41 μ m, crowdNumber volume is 3.03 × 10-3m3·kg-1。
To the results are summarized in table 2 and table 3. Wherein, the amount of the Fe in table, V and Mn is obtained hydrogenAmount in magnesium oxide particle.
[table 2]
[table 3]
Also can be clear and definite from the result of table 2 and table 3, magnesium hydroxide particle of the present invention be Lc be 0.5～1.5 μ m,Lc/d is more than 60%, flex point diameter is that 0.1～0.4 μ m, intergranular space are 0.6 × 10-3～1.0×10-3m3·kg-1Magnesium hydroxide particle. In addition, confirm using magnesium hydroxide particle of the present invention as interpolationAgent and resin carry out when mixing, compared with magnesium hydroxide particle in the past, and the large and good fluidity of eddy flow.On the other hand, the magnesium hydroxide particle of comparative example is as additive and resin when mixing, poor fluidity.
Utilizability in industry
Magnesium hydroxide particle of the present invention is not owing to containing subparticle, noncrystalline particle, and therefore particle is wholeBody is made up of the material of uniform crystal shape, therefore good to the compatibility of resin. As known from the above,The anti-flammability of magnesium hydroxide particle of the present invention and the mobility to resin and excellent dispersion. Therefore,In the semiconductor devices such as transistor, IC, LSI, be exceedingly useful as encapsulation with the packing material of resin.
Claims (8)
1. a magnesium hydroxide particle, its purity is more than 98 quality %, it is characterized in that habitFor hexagon prism shaped particles, described hexagon prism shaped particles is by the hexagon of 2 faces being up and down parallel to each otherThe corner post face of basal surface and 6 faces of periphery of forming between these basal surfaces forms, described hexagon prism shapeThe size of the c-axis direction of particle is 0.5～1.4 μ m, and the size of described c-axis direction is described hexagon prism shapeThe more than 60% of median particle diameter of grain, flex point diameter is 0.1～0.4 μ m, intergranular space is0.6×10-3～1.0×10-3m3·kg-1，
The Zeta potential of described magnesium hydroxide particle is-20～-25mV.
2. magnesium hydroxide particle according to claim 1, wherein, Fe content is 100～500ppm,V content is 30～250ppm, and Mn content is 10～150ppm.
3. magnesium hydroxide particle according to claim 1 and 2, wherein, the mode during pore distributes is straightFootpath is 0.1～0.3 μ m, and mode volume is 2.3 × 10-3～2.8×10-3m3·kg-1。
4. a manufacture method for magnesium hydroxide particle claimed in claim 1, it comprises following operation:
(a) in solvent, add magnesium hydroxide, iron compound, vfanadium compound and manganese compound and stir,Obtain the operation containing the slurry of magnesium hydroxide, iron, vanadium and manganese, with respect to magnesium hydroxide, the addition of ironThe addition that is 100～500ppm, vanadium is that the addition of 30～250ppm, manganese is 10～150ppm;
(b) by the slurries filtration containing magnesium hydroxide, iron, vanadium and manganese, washing dry, obtain hydrogen-oxygenChange the coarse grained operation of magnesium;
(c) by magnesium hydroxide coarse granule in air atmosphere, calcine at 800～1900 DEG C, obtainThe operation of magnesium oxide particle; And
(d) add magnesium oxide powder to having added in the warm water of organic acid below 100 DEG C, then at heightUnder shear agitation, carry out magnesian hydration reaction, the solid constituent that isolated by filtration generates then, goes forward side by sideRow washing, dry, obtains the operation of magnesium hydroxide particle thus, wherein, described magnesium oxide powder be byMagnesium oxide particle is pulverized and is sieved and obtains, and its median particle diameter is that 3～30 μ m, crystallite diameter are10×10-9More than m.
5. a resin combination, it contains
(I) epoxy resin,
(II) curing agent,
(III) inorganic filling material and
(IV) as the magnesium hydroxide particle described in any one in the claim 1～3 of fire retardant orThe magnesium hydroxide particle obtaining by manufacture method claimed in claim 4.
6. resin combination according to claim 5, wherein, the compounding of described magnesium hydroxide particleAmount is 1～35 quality % of described resin combination.
7. according to the resin combination described in claim 5 or 6, it is encapsulation agent for semiconductor.
8. a semiconductor device, its right to use requires the resin combination described in any one in 5～7.
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| PCT/JP2013/056720 WO2013146223A1 (en) | 2012-03-27 | 2013-03-12 | Magnesium hydroxide particles and resin composition containing same |
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| RU2561379C2 (en) * | 2013-10-29 | 2015-08-27 | Открытое Акционерное Общество "Каустик" | Magnesium hydroxide fire retardant nanoparticles and method for production thereof |
| JP6307352B2 (en) * | 2014-05-30 | 2018-04-04 | 京セラ株式会社 | Resin composition for optical semiconductor encapsulation and optical semiconductor device |
| WO2016043343A1 (en) * | 2014-09-18 | 2016-03-24 | 協和化学工業株式会社 | Colloidal-silica-coated magnesium hydroxide |
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| CN1854067A (en) * | 2005-04-28 | 2006-11-01 | 达泰豪化学工业株式会社 | Magnesium hydrate particles and its manufacturing method and resin composite including same |
| CN101223235A (en) * | 2005-07-13 | 2008-07-16 | 日立化成工业株式会社 | Epoxy resin composition for encapsulation and electronic part device |
| CN101687659A (en) * | 2007-06-27 | 2010-03-31 | 达泰豪化学工业株式会社 | Magnesium oxide particle aggregate, and method for production thereof |
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| WO2000035808A1 (en) * | 1998-12-14 | 2000-06-22 | Kyowa Chemical Industry Co., Ltd. | Magnesium hydroxide particles, process for producing the same, and resin composition containing the particles |
| JP4365987B2 (en) * | 2000-05-15 | 2009-11-18 | 協和化学工業株式会社 | LAMINATED MATERIAL AND ELECTRIC AND ELECTRONIC DEVICE RESIN COMPOSITION AND MOLDED ARTICLE THEREOF |
| US6899768B2 (en) * | 2000-10-25 | 2005-05-31 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide particle aggregate |
| JP4611138B2 (en) * | 2003-10-21 | 2011-01-12 | 宇部マテリアルズ株式会社 | Method for producing magnesium oxide vapor deposition material |
| JP4745713B2 (en) * | 2005-04-28 | 2011-08-10 | タテホ化学工業株式会社 | Magnesium hydroxide particles, method for producing the same, and resin composition containing the same |
| JP5069865B2 (en) * | 2006-03-27 | 2012-11-07 | タテホ化学工業株式会社 | High purity magnesium hydroxide powder and method for producing the same |
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| CN1854067A (en) * | 2005-04-28 | 2006-11-01 | 达泰豪化学工业株式会社 | Magnesium hydrate particles and its manufacturing method and resin composite including same |
| CN101223235A (en) * | 2005-07-13 | 2008-07-16 | 日立化成工业株式会社 | Epoxy resin composition for encapsulation and electronic part device |
| CN101687659A (en) * | 2007-06-27 | 2010-03-31 | 达泰豪化学工业株式会社 | Magnesium oxide particle aggregate, and method for production thereof |
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| KR20140139096A (en) | 2014-12-04 |
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